EP0028756A2 - Process for dyeing polyamide fibres - Google Patents
Process for dyeing polyamide fibres Download PDFInfo
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- EP0028756A2 EP0028756A2 EP80106575A EP80106575A EP0028756A2 EP 0028756 A2 EP0028756 A2 EP 0028756A2 EP 80106575 A EP80106575 A EP 80106575A EP 80106575 A EP80106575 A EP 80106575A EP 0028756 A2 EP0028756 A2 EP 0028756A2
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/06—Material containing basic nitrogen containing amide groups using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/56—Condensation products or precondensation products prepared with aldehydes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
- D06P1/621—Compounds without nitrogen
- D06P1/622—Sulfonic acids or their salts
- D06P1/625—Aromatic
Definitions
- alkyl radicals R which may be mentioned are the tert.-butyl, octyl, nonyl or dodecyl radicals, and alkoxy radicals which are the methoxy, ethoxy, propoxy, isopropoxy, butoxy or hexyloxy radical.
- Suitable hydroxyalkoxy radicals are, for example, the 2-hydroxyethoxy radical, 2-hydroxypropoxy radical, 2-hydroxybutoxy radical or 2-hydroxy-decylocyrest.
- the radical R can be in the o-, m- or p-position to the phenolic hydroxyl group.
- Compounds to be used preferably contain it in the p-position.
- the methylene group is then connected to the benzene ring in the o, o 'position.
- alkyl radicals R 1 which may be mentioned are the methyl, ethyl, propyl or isopropyl radical.
- alkaline earth metal ions such as magnesium or calcium or preferably monovalent cations
- ammonium ion or substituted ammonium ions such as the ethylammonium ion, butylammonium ion, cyclohexylammonium ion, hydroxyethylammonium ion, bishydroxyethylammonium ion, trishydroxyethylammonium ion, bis-hydroxypropylammonium ion -ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium or ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium
- the compound of the formula I can be prepared in a manner known per se by reacting the corresponding phenols with formaldehyde or lower aldehydes such as isobutyraldehyde in the presence of acidic catalysts such as sulfuric acid, toluenesulfonic acid or boron fluoride.
- acidic catalysts such as sulfuric acid, toluenesulfonic acid or boron fluoride.
- the molecular weight of the condensation products obtained or the degree of polymerization n is essentially determined by the molar ratio of phenolic compound to aldehyde.
- the preparation of the condensation products is described for example in DE-OS 2 306 104.
- the sulfonation is carried out in a known manner using, for example, oleum, sulfur trioxide or chlorosulfonic acid, if appropriate in inert solvents. The sulfonation is e.g. described in DE-OS 1 090 966.
- Preferred compounds for the dyeing process according to the invention are those compounds of the formula I or their salts in which R represents an alkyl radical containing 4-12, in particular 8 or 9, carbon atoms or the cyclohexyl radical, R 1 represents hydrogen, n is a number from 2 to 5 means, and m represents 2 to 5.
- the compounds are preferably used in the form of their lithium, sodium, potassium, ammonium or ammonium salts substituted by hydroxyethyl or hydroxypropyl groups.
- the dyeing of the polyamide materials with metal complex dyes and / or acid dyes in the presence of the compounds I can be carried out in such a way that the material to be dyed is introduced into an aqueous liquor heated to 40-50 ° C. which contains the metal complex dyes and / or acid dyes, the compounds to be used according to the invention of formula I and acids, e.g. Acetic acid, then increases the temperature of the dyebath gradually to 100 - 130 ° C and keeps it at this temperature until it is exhausted. It has proven to be particularly advantageous to pretreat the material to be dyed with an aqueous liquor which only contains the compounds and acids containing sulfonic acid groups for a short time at 40-50 ° C. and only then to treat the liquor at temperatures between 40 and 98 ° C. Add dyes, then gradually raise the temperature of the dyebath to 100 - 130 ° C and keep it at this temperature until exhaustion.
- the compounds to be used according to the invention of formula I and acids e.g. Acetic
- the amounts in which the compounds of the formula I are added to the dyeing baths can vary within wide limits; they can easily be determined by preliminary tests. In general, depending on the desired depth of color, quantities of 0.5-3 percent by weight, based on the weight of the material to be dyed, have proven successful.
- the dyeing process is suitable for natural polyamides, such as wool and silk, and in particular for dyeing syn theoretical polyamides, such as polycaprolactam, polyhexamethylene diamine adipate or poly- ⁇ -aminoundecanoic acid with 1: 2 metal complex dyes.
- Suitable dyes are described, for example, in Color Index 3rd Edition (1971) Vol. 1.
- a polyamide knitted fabric made of filament threads is introduced in a liquor ratio of 1:15 into a bath heated to 40 ° C. and adjusted to pH 8 with a mixture of monosodium hydrogenphosphate and tetrasodium pyrophosphate, which contains in liter 0.24 9 of the compound described below.
- the material is treated while the bath is heated to 98-115 ° C and then 0.4 g of the chromium (1: 2) complex is added per liter to.
- Example 1 The coloring described in Example 1 is carried out in the same way. Instead of the compound added there, however, 0.24 part of the condensation product described below is added. This also results in an excellent level bordo coloring.
- the condensation product used was prepared as follows: 264 parts of p-cyclohexylphenol and 1 part of concentrated sulfuric acid are mixed with 300 parts of xylene and 100 - 110 ° C slowly mixed with 82 parts of 36.5% aqueous formaldehyde. The water is distilled off simultaneously via a water separator. The xylene is distilled off in vacuo, the resin obtained (molecular weight 600) is dissolved in 500 parts of trichlorethylene, and 130 parts of chlorosulfonic acid are slowly added at 10-20 ° C.
- the mixture is stirred for 12 hours at room temperature and 30 minutes at 50 ° C and neutralized at 20 - 40 ° C with 130 parts of 45% sodium hydroxide solution. Concentration in vacuo gives about 410 parts of a viscous resin which, after cooling, can be pulverized into a water-soluble, white product.
- the dyeing can be carried out with equal success if, instead of the condensation product mentioned, a p-tert in the same way consists of 225 parts. Butylphenol, 32 parts 36.5% formaldehyde, 1 g conc. Sulfuric acid (molecular weight 500), 114 parts of chlorosulfonic acid and 86 parts of 25% aqueous ammonia-produced condensation product is used.
- a knitted fabric made of ⁇ -polycaprolactam is heated in a 1:40 liquor ratio to a temperature of 50 ° C. and with Trisodium phosphate, pH 8, was introduced, which contains 0.3 g per liter of the condensation product described below.
- the material is treated while the bath is heated to 98 ° C. and 0.125 g of the chromium (1: 2) complex is then per liter to. After dyeing at 98 ° C. for about 90 minutes, the liquor is exhausted. A light gray coloration of excellent uniformity is obtained.
- the condensation product used is in the manner given in Example 1 from 330 parts of nonylphenol, 94 parts of 37% formaldehyde solution, 1 part of conc. Sulfuric acid (molecular weight 1150), 330 parts of cyclohexane and 166.5 parts of chlorosulfonic acid. Instead of the sodium hydroxide solution, 200 parts of triethanolamine were used for neutralization.
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- Textile Engineering (AREA)
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Abstract
Das Färben von Polyamidfasermaterialien mit Säure- und/oder Metallkomplexfarbstoffen wird in Gegenwart von Verbindungen der Formel <IMAGE> in der R für einen C4-C12-Alkyl- C1-C12-Alkoxy-, Phenyl-, Cyclohexyl- oder C2-C10-Hydroxy-alkoxyrest, R' für Wasserstoff oder einen C1-C4-Alkylrest, n für ganze Zahlen von 1 bis 10 und m für Zahlen von 1 bis n + 1 stehen, oder deren wasserlöslichen Salzen durchgeführt.The dyeing of polyamide fiber materials with acid and / or metal complex dyes is carried out in the presence of compounds of the formula <IMAGE> in the R for a C4-C12-alkyl-C1-C12-alkoxy, phenyl, cyclohexyl or C2-C10-hydroxy alkoxy radical, R 'is hydrogen or a C1-C4-alkyl radical, n are integers from 1 to 10 and m is from 1 to n + 1, or their water-soluble salts are carried out.
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Färben von Polyamidfasermaterialien mit Säurefarbstoffen und Metallkomplexfarbstoffen, dadurch gekennzeichnet, daß man die Färbung in Gegenwart von Verbindungen der allgemeinen Formel
durchführt, wobei
- R für einen C4-C12 Alkyl-, C1-C12-Alkoxy, Phenyl-Cyclohexyl- oder C2-C10-Hydroxyalkoxyrest,
- R1 für Wasserstoff oder einen C1-C4-Alkylrest, n für ganze Zahlen von 1 bis 10 und
- m für Zahlen von 1 bis n + 1 stehen.
performs, where
- R is a C 4 -C 12 alkyl, C 1 -C 12 alkoxy, phenyl-cyclohexyl or C 2 -C 10 hydroxyalkoxy radical,
- R 1 represents hydrogen or a C 1 -C 4 alkyl radical, n for integers from 1 to 10 and
- m stand for numbers from 1 to n + 1.
Als Alkylreste R seien beispielsweise der tert.Butyl-, Octyl-, Nonyl- oder Dodecylrest, als Alkoxyreste der Methoxy-, Ethoxy-, Propoxy-, Isopropoxy, Butoxy, oder Hexyloxyrest genannt. Geeignete Hydroxyalkoxyreste sind beispielsweise der 2-Hydroxyethoxyrest, 2-Hydroxypropoxyrest, 2-Hydroxybutoxyrest oder 2-Hydroxy-decylocyrest.Examples of alkyl radicals R which may be mentioned are the tert.-butyl, octyl, nonyl or dodecyl radicals, and alkoxy radicals which are the methoxy, ethoxy, propoxy, isopropoxy, butoxy or hexyloxy radical. Suitable hydroxyalkoxy radicals are, for example, the 2-hydroxyethoxy radical, 2-hydroxypropoxy radical, 2-hydroxybutoxy radical or 2-hydroxy-decylocyrest.
Der Rest R kann in o-, m- oder p-Stellung zur phenolischen Hydroxylgruppe stehen. Bevorzugt zu verwendende Verbindungen enthalten ihn in p-Stellung. Die Methylengruppe ist dann in o-, o'-Stellung mit dem Benzolring verbunden.The radical R can be in the o-, m- or p-position to the phenolic hydroxyl group. Compounds to be used preferably contain it in the p-position. The methylene group is then connected to the benzene ring in the o, o 'position.
Als Alkylreste R1 seien beispielsweise der Methyl-, Ethyl-, Propyl- oder Isopropylrest genannt.Examples of alkyl radicals R 1 which may be mentioned are the methyl, ethyl, propyl or isopropyl radical.
Als salzbildende Kationen für die Sulfonsäuren der Formel I können Erdalkalimetallionen, wie Magensium oder Calcium oder vorzugsweise einwertige Kationen,As salt-forming cations for the sulfonic acids of the formula I, alkaline earth metal ions, such as magnesium or calcium or preferably monovalent cations,
wie die Ionen der Alkalimetalle Lithium, Natrium oder Kalium, das Ammoniumion oder substituierte Ammoniumionen, wie das Ethylammoniumion, Butylammoniumion, Cyclohexylammoniumion, Hydroxyethylammoniumion, Bishydroxyethylammoniumion, Trishydroxyethyl-ammoniumion, Bis-hydroxypropylammoniumion, oder auch quarternäre Ammoniumionen, wie das Bis-hydroxyethyl-dimethylammoniumion oder das Trimethyl-cyclohexylammoniumion, verwendet werden.such as the ions of the alkali metals lithium, sodium or potassium, the ammonium ion or substituted ammonium ions, such as the ethylammonium ion, butylammonium ion, cyclohexylammonium ion, hydroxyethylammonium ion, bishydroxyethylammonium ion, trishydroxyethylammonium ion, bis-hydroxypropylammonium ion -ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium or ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-bis-ammonium-bis-ammonium-bis-ammonium-bis-ammonium-bis-ammonium-bis-ammonium-bis-ammonium-ammonium-bis-ammonium-bis-ammonium-ammonium-ammonium-bis-ammonium-ammonium-bis-ammonium-bis-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ion-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium-ammonium, ion or the trimethyl-cyclohexylammonium ion can be used.
Die Herstellung der Verbindung der Formel I kann in an sich bekannter Weise durch Umsetzung der entsprechenden Phenole mit Formaldehyd oder niederen Aldehyden wie Isobutyraldehyd in Gegenwart von sauren Katalysatoren, wie Schwefelsäure, Toluolsulfonsäure oder Borfluorid erfolgen. Das Molgewicht der erhaltenen Kondensationsprodukte bzw. der Polymerisationsgrad n, wird im wesent- - lichen durch das Molverhältnis von phenolischer Verbindung zu Aldehyd bestimmt. Die Herstellung der Kondensationsprodukte wird beispielsweise in der DE-OS 2 306 104 beschrieben. Die Sulfonierung wird in bekannter Weise unter Verwendung von beispielsweise Oleum, Schwefeltrioxid oder Chlorsulfonsäure gegebenenfalls in inerten Lösungsmitteln durchgeführt. Die Sulfonierung wird z.B. in der DE-OS 1 090 966 beschrieben.The compound of the formula I can be prepared in a manner known per se by reacting the corresponding phenols with formaldehyde or lower aldehydes such as isobutyraldehyde in the presence of acidic catalysts such as sulfuric acid, toluenesulfonic acid or boron fluoride. The molecular weight of the condensation products obtained or the degree of polymerization n is essentially determined by the molar ratio of phenolic compound to aldehyde. The preparation of the condensation products is described for example in DE-OS 2 306 104. The sulfonation is carried out in a known manner using, for example, oleum, sulfur trioxide or chlorosulfonic acid, if appropriate in inert solvents. The sulfonation is e.g. described in DE-OS 1 090 966.
Bevorzugte Verbindungen für das erfindungsgemäße Färbeverfahren sind solche Verbindungen der Formel I oder deren Salze, in denen R für einen 4 - 12 insbesondere 8 oder 9 Kohlenstoffatome enthaltenden Alkylrest oder für den Cyclohexylrest steht, R1 für Wasserstoff steht, n eine Zahl von 2 bis 5 bedeutet, und m für 2 bis 5 steht. Die Verbindungen werden vorzugsweise in Form ihrer Lithium-, Natrium-, Kalium-, Ammonium- oder durch Hydroxyethyl- oder Hydroxypropylgruppen substituierter Ammoniumsalze eingesetzt.Preferred compounds for the dyeing process according to the invention are those compounds of the formula I or their salts in which R represents an alkyl radical containing 4-12, in particular 8 or 9, carbon atoms or the cyclohexyl radical, R 1 represents hydrogen, n is a number from 2 to 5 means, and m represents 2 to 5. The compounds are preferably used in the form of their lithium, sodium, potassium, ammonium or ammonium salts substituted by hydroxyethyl or hydroxypropyl groups.
Das Färben der Polyamidmaterialien mit Metallkomplexfarbstoffen und/oder Säurefarbstoffen in Gegenwart der Verbindungen I kann so durchgeführt werden, daß man das Färbegut in eine auf 40 - 50°C erwärmte wäßrige Flotte einbringt, die die Metallkomplexfarbstoffe und/ oder Säurefarbstoffe, die erfindungsgemäß zu verwendenden Verbindungen der Formel I und Säuren, z.B. Essigsäure, enthält, dann die Temperatur des Färbebades allmählich auf 100 - 130°C steigert und so lange auf dieser Temperatur hält, bis es erschöpft ist. Als be- _ sonders vorteilhaft hat es sich erwiesen, das Färbegut mit einer wäßrigen Flotte, die nur die sulfonsäuregruppenhaltige Verbindungen und Säuren enthält, kurze Zeit bei 40 - 50°C vorzubehandeln und erst dann der Flotte bei Temperaturen zwischen 40 und 98°C die Farbstoffe zuzusetzen, anschließend die Temperatur des Färbebades allmählich auf 100 - 130°C zu steigern und bis zur Erschöpfung auf dieser Temperatur zu halten.The dyeing of the polyamide materials with metal complex dyes and / or acid dyes in the presence of the compounds I can be carried out in such a way that the material to be dyed is introduced into an aqueous liquor heated to 40-50 ° C. which contains the metal complex dyes and / or acid dyes, the compounds to be used according to the invention of formula I and acids, e.g. Acetic acid, then increases the temperature of the dyebath gradually to 100 - 130 ° C and keeps it at this temperature until it is exhausted. It has proven to be particularly advantageous to pretreat the material to be dyed with an aqueous liquor which only contains the compounds and acids containing sulfonic acid groups for a short time at 40-50 ° C. and only then to treat the liquor at temperatures between 40 and 98 ° C. Add dyes, then gradually raise the temperature of the dyebath to 100 - 130 ° C and keep it at this temperature until exhaustion.
Die Mengen, in denen die Verbindungen der Formel I den Färbenädern zugesetzt werden, können in weiten Grenzen schwanken; sie lassen sich durch Vorversuche leicht ermitteln. Im allgemeinen haben sich je nach der gewünschten Farbtiefe Mengen von 0,5 - 3 Gewichtsprozent, bezogen auf das Gewicht des Färbegutes, bewährt.The amounts in which the compounds of the formula I are added to the dyeing baths can vary within wide limits; they can easily be determined by preliminary tests. In general, depending on the desired depth of color, quantities of 0.5-3 percent by weight, based on the weight of the material to be dyed, have proven successful.
Das Färbeverfahren eignet sich für natürliche Polyamide, wie Wolle und Seide, und insbesondere zum Färben von synthetischen Polyamiden, wie Polycaprolactam, Polyhexamethylendiamin-adipat oder Poly- ω-aminoundecansäure mit 1:2-Metallkomplexfarbstoffen.The dyeing process is suitable for natural polyamides, such as wool and silk, and in particular for dyeing syn theoretical polyamides, such as polycaprolactam, polyhexamethylene diamine adipate or poly-ω-aminoundecanoic acid with 1: 2 metal complex dyes.
Geeignete Farbstoffe sind beispielsweise in Colour Index 3. Auflage (1971) Bd. 1 beschrieben.Suitable dyes are described, for example, in Color Index 3rd Edition (1971) Vol. 1.
Mit Hilfe des erfindungsgmäßen Verfahrens gelingt es, Polyamidfasermaterialien in den verschiedensten Verarbeitungsformen, beispielsweise als Flocke, Kammzug, texturierte Fäden, Spinnkabel, Garn, Gewebe, Gewirke oder Vlies mit Metallkomplexfarbstoffen und/oder Säurefarbstoffen hervorragend gleichmäßig zu färben; insbesondere wird das beim Färben von Geweben oder Gewirken aus synthetischen Polyamiden leicht auftretende Streifigfärben vermieden.With the aid of the method according to the invention, it is possible to dye polyamide fiber materials in a wide variety of processing forms, for example as a flake, sliver, textured threads, spun cord, yarn, fabric, knitted fabric or fleece, with metal complex dyes and / or acid dyes in an outstandingly uniform manner; in particular, the streaky dyeing which occurs easily when dyeing fabrics or knitted fabrics made of synthetic polyamides is avoided.
Die in den nachfolgenden Beispielen angegebenen Teile sind Gewichtsteile.The parts given in the following examples are parts by weight.
Eine Polyamid-Wirkware aus Filamentfäden wird im Flottenverhältnis 1:15 in ein auf 40°C erwärmtes und mit einer Mischung aus Mononatriumhydrogenphosphat und Tetranatriumpyrophosphat auf den pH-Wert 8 eingestelltes Bad eingebracht, das im Liter 0,24 9der nachstehend beschriebenen Verbindung enthält. Man behandelt darin das Material unter Erwärmung des Bades bis auf 98 - 115°C und setzt dann pro Liter 0,4 g des Chrom-(1:2)-Komplexes von
Nach einer Färbezeit von 60 - 120 Minuten bei 98°C ist die Flotte erschöpft. Es resultiert eine Bordofärbung mit hoher Egalität. Blaue Färbungen mit hoher Egalität werden erhalten, wenn man den Chromkomplex durch die gleiche Menge des Farbstoffs der DE-AS 1 644 600, Beispiel 1, der DE-AS 1 932 647,Beispiel 1A und der DE-OS 2 508 506 ersetzt.After a dyeing time of 60-120 minutes at 98 ° C, the liquor is exhausted. The result is a bordo coloring with high levelness. Blue colorations with high levelness are obtained if the chromium complex is replaced by the same amount of the dye of DE-AS 1 644 600, example 1, DE-AS 1 932 647, example 1A and DE-OS 2 508 506.
Die verwendete Verbindung wurde auf folgende Weise hergestellt:
- 1320 Teile Nonylphenol und 1 Teil konz. Schwefelsäure werden bei 90 - 100°C innerhalb von 1- 2 Stunden mit 332 Teilen 36 %iger wäßriger Formaldehydlösung versetzt. Es wird 2 Stunden bei 90 - 100°C nachgerührt und dann das Wasser im Vakuum abdestilliert. Das erhaltene Harz (Molekulargewicht 700) wird in 1000 Teilen Cyclohexan aufgenommen und bei 10 - 20°C langsam mit 650 Teilen Chlorsulfonsäure versetzt. Man rührt 20 Stunden bei Raumtemperatur und neutralisiert anschließend unter Zugabe von 650 Teilen 45 %iger Natronlauge. Das Cyclohexan und das Wasser werden anschließend im Rotationsverdampfer abdestilliert. Es werden ca. 2000 Teile eines Harzes erhalten, das sich nach dem Abkühlen zu einem wasserlöslichen Produkt pulverisieren läßt.
- 1320 parts of nonylphenol and 1 part of conc. 332 parts of 36% strength aqueous formaldehyde solution are added to sulfuric acid at 90-100 ° C. within 1-2 hours. The mixture is stirred at 90-100 ° C. for 2 hours and then the water is distilled off in vacuo. The resin obtained (molecular weight 700) is taken up in 1000 parts of cyclohexane and slowly mixed with 650 parts of chlorosulfonic acid at 10-20 ° C. The mixture is stirred for 20 hours at room temperature and then neutralized with the addition of 650 parts of 45% sodium hydroxide solution. The cyclohexane and the water are then distilled off in a rotary evaporator. About 2000 parts of a resin are obtained which, after cooling, can be pulverized into a water-soluble product.
Die in Beispiel 1 beschriebene Färbung wird in gleicher Weise durchgeführt. An Stelle der dort zugesetzten Verbindung werden jedoch 0,24 Teile des nachfolgend beschriebenen Kondensationsproduktes zugesetzt. Es resultiert ebenfalls eine hervorragend egale Bordofärbung. Das eingesetzte Kondensationsprodukt wurde wie folgt hergestellt: 264 Teile p-Cyclohexylphenol und 1 Teil konz.Schwefelsäure werden mit 300 Teilen Xylol vermischt und bei 100 - 110°C langsam mit 82 Teilen 36,5 %igem wäßrigen Formaldehyd versetzt. Das Wasser wird gleichzeitig über einen Wasserabscheider abdestilliert. Das Xylol wird im Vakuum abdestilliert, das erhaltene Harz (Molekulargewicht 600) in 500 Teilen Trichlorethylen gelöst und bei 10 - 20°C mit 130 Teilen Chlorsulfonsäure langsam versetzt. Man rührt 12 Stunden bei Raumtemperatur und 30 Minuten bei 50°C nach und neutralisiert bei 20 - 40°C mit 130 Teilen 45 %iger Natronlauge. Durch Einengen im Vakuum werden ca. 410 Teile eines viskosen Harzes erhalten, das sich nach dem Abkühlen zu einem wasserlöslichen, weißen Produkt pulverisieren läßt.The coloring described in Example 1 is carried out in the same way. Instead of the compound added there, however, 0.24 part of the condensation product described below is added. This also results in an excellent level bordo coloring. The condensation product used was prepared as follows: 264 parts of p-cyclohexylphenol and 1 part of concentrated sulfuric acid are mixed with 300 parts of xylene and 100 - 110 ° C slowly mixed with 82 parts of 36.5% aqueous formaldehyde. The water is distilled off simultaneously via a water separator. The xylene is distilled off in vacuo, the resin obtained (molecular weight 600) is dissolved in 500 parts of trichlorethylene, and 130 parts of chlorosulfonic acid are slowly added at 10-20 ° C. The mixture is stirred for 12 hours at room temperature and 30 minutes at 50 ° C and neutralized at 20 - 40 ° C with 130 parts of 45% sodium hydroxide solution. Concentration in vacuo gives about 410 parts of a viscous resin which, after cooling, can be pulverized into a water-soluble, white product.
Mit gleichem Erfolg läßt sich die Färbung durchführen, wenn an Stelle des genannten Kondensationsproduktes ein in gleicher Weise aus 225 Teilen p-tert. Butylphenol, 32 Teile 36,5 %igem Formaldehyd, 1 g konz. Schwefelsäure (Molekulargewicht 500), 114 Teilen Chlorsulfonsäure und 86 Teile 25 %igem wäßrigen Ammoniak hergestelltes Kondensationsprodukt verwendt wird.The dyeing can be carried out with equal success if, instead of the condensation product mentioned, a p-tert in the same way consists of 225 parts. Butylphenol, 32 parts 36.5% formaldehyde, 1 g conc. Sulfuric acid (molecular weight 500), 114 parts of chlorosulfonic acid and 86 parts of 25% aqueous ammonia-produced condensation product is used.
Ein Gewirk aus ε-Polycaprolactam wird im Flottenverhältnis 1:40 in ein auf 50°C erwärmtes und mit Trinatriumphosphat auf pH-Wert 8 eingestelltes Bad eingebracht, das im Liter 0,3 g des nachfolgend beschriebenen Kondensationsproduktes enthält. Man behandelt darin das Material unter Erwärmung des Bades auf 98°C und setzt dann pro Liter 0,125 g des Chrom (1:2)-Komplexes von
Das verwendete Kondensationsprodukt wird in der in Beispiel 1 angegebenen Weise aus 330 Teilen Nonylphenol, 94 Teilen 37 %iger Formaldehydlösung, 1 Teil konz. Schwefelsäure (Molekulargewicht 1150), 330 Teilen Cyclohexan und 166,5 Teilen Chlorsulfonsäure hergestellt. An Stelle der Natronlauge wurden zur Neutralisation 200 Teile Triethanolamin verwendet.The condensation product used is in the manner given in Example 1 from 330 parts of nonylphenol, 94 parts of 37% formaldehyde solution, 1 part of conc. Sulfuric acid (molecular weight 1150), 330 parts of cyclohexane and 166.5 parts of chlorosulfonic acid. Instead of the sodium hydroxide solution, 200 parts of triethanolamine were used for neutralization.
Claims (3)
oder deren wasserlöslichen Salzen durchführt.1. A process for dyeing polyamide fiber materials with acid and / or metal complex dyes, characterized in that the dyeing in the presence of compounds of the formula
or carries out their water-soluble salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2945102 | 1979-11-08 | ||
| DE19792945102 DE2945102A1 (en) | 1979-11-08 | 1979-11-08 | METHOD FOR DYING POLYAMIDE FIBERS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0028756A2 true EP0028756A2 (en) | 1981-05-20 |
| EP0028756A3 EP0028756A3 (en) | 1981-06-03 |
| EP0028756B1 EP0028756B1 (en) | 1983-07-20 |
Family
ID=6085473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80106575A Expired EP0028756B1 (en) | 1979-11-08 | 1980-10-25 | Process for dyeing polyamide fibres |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4295852A (en) |
| EP (1) | EP0028756B1 (en) |
| JP (1) | JPS5673180A (en) |
| DE (2) | DE2945102A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0102926A1 (en) * | 1982-09-03 | 1984-03-14 | Ciba-Geigy Ag | Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibres |
| DE3442888A1 (en) * | 1983-12-05 | 1985-06-13 | Sandoz-Patent-GmbH, 7850 Lörrach | Dyeing auxiliary based on novolak compounds |
| US5470355A (en) * | 1983-12-05 | 1995-11-28 | Sandoz Ltd. | Organic compounds |
| CN103243582A (en) * | 2013-04-16 | 2013-08-14 | 杜芳莉 | Acidic levelling agent and preparation method thereof |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3673008D1 (en) * | 1983-12-16 | 1990-08-30 | Monsanto Co | Stain-resistant NYLON CARPETS. |
| US4592940A (en) * | 1983-12-16 | 1986-06-03 | Monsanto Company | Stain-resistant nylon carpets impregnated with condensation product of formaldehyde with mixture of diphenolsulfone and phenolsulfonic acid |
| US4619853A (en) * | 1983-12-21 | 1986-10-28 | Monsanto Company | Easy-clean carpets which are stain resistant and water impervious |
| US4501591A (en) * | 1983-12-27 | 1985-02-26 | Monsanto Company | Process for conveniently providing stain-resistant polyamide carpets |
| US4839212A (en) * | 1986-03-06 | 1989-06-13 | Monsanto Company | Stain resistant nylon carpets |
| US4879180A (en) * | 1986-03-06 | 1989-11-07 | Monsanto Company | Stain-resistant nylon fibers |
| EP0242496B1 (en) * | 1986-03-06 | 1991-12-27 | Monsanto Company | Stain-resistant nylon fibers |
| US4800118A (en) * | 1987-11-04 | 1989-01-24 | West Point Pepperell | Compositions and methods for imparting stain resistance to textile articles |
| JPH02262862A (en) * | 1989-02-22 | 1990-10-25 | Matsushita Electric Ind Co Ltd | Brushless motor |
| JPH02269452A (en) * | 1989-04-07 | 1990-11-02 | Matsushita Electric Ind Co Ltd | Brushless motor |
| AU684991B2 (en) * | 1994-08-08 | 1998-01-08 | Wool Research Organisation Of New Zealand Inc. | A method of preventing photobleaching of wool and/or other natural fibres |
| CN104532620A (en) * | 2014-12-24 | 2015-04-22 | 常熟市淼泉盛达助剂厂 | Levelling agent for wool and real silk |
| CN104532621A (en) * | 2014-12-24 | 2015-04-22 | 常熟市淼泉盛达助剂厂 | Dispersing and leveling agent for fabrics |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH355125A (en) * | 1958-11-14 | 1961-06-30 | Ciba Geigy | Preparation suitable for dyeing wool |
| US3118723A (en) * | 1961-02-08 | 1964-01-21 | Arthur J I Harding | Process for dyeing nylon to produce multi-colored dyeings |
| DE1793299A1 (en) * | 1968-08-28 | 1972-02-17 | Bayer Ag | Sulfonation products |
| DE2328767A1 (en) * | 1972-06-15 | 1974-01-10 | Ciba Geigy Ag | CONDENSATION PRODUCTS CONTAINING SULFURIC ACID |
| FR2398835A1 (en) * | 1977-07-28 | 1979-02-23 | Protex Manuf Prod Chimiq | Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1769613A1 (en) * | 1968-06-15 | 1971-07-01 | Bayer Ag | Agent for improving the wet fastness properties of dyes produced with cationic dyes on synthetic polyamides |
| BE759823A (en) * | 1969-12-03 | 1971-05-17 | Bayer Ag | AGENTS IMPROVING WET SOLIDITY |
| US3993439A (en) * | 1970-07-03 | 1976-11-23 | Hoechst Aktiengesellschaft | Dispersing and stabilizing agents for dyestuffs |
| BE795961A (en) * | 1972-02-25 | 1973-08-27 | Hoechst Ag | APPLICATION OF SULPHURIC HEMI-ESTERS TO DISPERSION OF COLORANTS |
-
1979
- 1979-11-08 DE DE19792945102 patent/DE2945102A1/en not_active Withdrawn
-
1980
- 1980-10-25 DE DE8080106575T patent/DE3064313D1/en not_active Expired
- 1980-10-25 EP EP80106575A patent/EP0028756B1/en not_active Expired
- 1980-11-03 US US06/202,907 patent/US4295852A/en not_active Expired - Lifetime
- 1980-11-06 JP JP15525980A patent/JPS5673180A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH355125A (en) * | 1958-11-14 | 1961-06-30 | Ciba Geigy | Preparation suitable for dyeing wool |
| US3118723A (en) * | 1961-02-08 | 1964-01-21 | Arthur J I Harding | Process for dyeing nylon to produce multi-colored dyeings |
| DE1793299A1 (en) * | 1968-08-28 | 1972-02-17 | Bayer Ag | Sulfonation products |
| DE2328767A1 (en) * | 1972-06-15 | 1974-01-10 | Ciba Geigy Ag | CONDENSATION PRODUCTS CONTAINING SULFURIC ACID |
| FR2398835A1 (en) * | 1977-07-28 | 1979-02-23 | Protex Manuf Prod Chimiq | Fixing agent for dyes on polyamide fibres - consists of phenolic novolak resin with low free phenol content |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Bd. 72, Nr. 12, 23 März 1970, Columbus, Ohio, US; Zusammenfassung Nr. 56634P, Seite 63; & JP 44 020513 B1 (MEISEI CHEMICAL WORKS) 03 September 1969 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0102926A1 (en) * | 1982-09-03 | 1984-03-14 | Ciba-Geigy Ag | Dyeing auxiliary and its use in dyeing or printing synthetic polyamide fibres |
| DE3442888A1 (en) * | 1983-12-05 | 1985-06-13 | Sandoz-Patent-GmbH, 7850 Lörrach | Dyeing auxiliary based on novolak compounds |
| US5470355A (en) * | 1983-12-05 | 1995-11-28 | Sandoz Ltd. | Organic compounds |
| CN103243582A (en) * | 2013-04-16 | 2013-08-14 | 杜芳莉 | Acidic levelling agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61476B2 (en) | 1986-01-08 |
| EP0028756A3 (en) | 1981-06-03 |
| US4295852A (en) | 1981-10-20 |
| JPS5673180A (en) | 1981-06-17 |
| DE3064313D1 (en) | 1983-08-25 |
| DE2945102A1 (en) | 1981-05-14 |
| EP0028756B1 (en) | 1983-07-20 |
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